TW201027261A - Wet-etchable antireflective coatings - Google Patents

Abstract

Antireflective coatings produced from silsesquioxane resin is comprised of the units (Ph(CH2)rSiO(3-x)/2(OR')x)m (HSiO(3-x)/2(OR')x)n (MeSiO(3-x)/2(OR')x)o (RSiO(3-x)/2(OR')x)p (R1SiO(3-x)/2(OR')x)q where Ph is a phenyl group, Me is a methyl group; R' is hydrogen atom or a hydrocarbon group having from 1 to 4 carbon atoms; R is selected from a carboxylic acid group or a carboxylic acid forming group with the proviso that there is a sufficient amount of carboxylic acid groups to make the resin wet etchable after cure; and R1 is selected from substituted phenyl groups, ester groups, polyether groups; mercapto groups, sulfur-containing organic functional groups, hydroxyl producing group, aryl sulphonic ester groups, and reactive or curable organic functional groups; and r has a value of 0, 1, 2, 3, or 4; x has a value of 0, 1 or 2; wherein in the resin m has a value of 0 to 0.90; n has a value of 0.05 to 0.99; o has a value of 0 to 0.95; p has a value of 0.01 to 0.5; q has a value of 0 to 0.5; and m + n + o + p + q ≈ 1.

Description

201027261 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an antireflection coating made of a sesquioxane resin. [Prior Art] With continued demand for smaller feature sizes in the semiconductor industry, 193 nm lithography has recently emerged as a technique for producing devices having sub-100 nm characteristics. The use of this shorter wavelength light requires a bottom anti-reflective coating (BARC) to reduce reflection on the substrate and to slow the oscillating cure of the photoresist by absorbing light passing through the photoresist. Commercially available anti-reflective coatings are composed of two materials based on organic and inorganic. In general, inorganic ARC exhibiting good etch resistance is based on CVD and is limited by all the integration disadvantages of extreme surface configurations; on the other hand, organic ARC materials are applied by a spin coating process with excellent filling and planarity. Properties, but suffer from poor etch selectivity of organic photoresists. Therefore, there is a high need for a material that provides the advantages of integrated organic and inorganic ARC. In this regard, it has recently been found that certain phenyl-hydrides based on sesquiterpene oxide resins exhibit excellent anti-reflective coating properties for 193 nm light. While the bottom anti-reflective coating (BARC) material is effective in reducing the reflection of the activating radiation, removing the BARC material without damaging the upper photoresist and/or the underlying substrate has been quite challenging. A typical method for removing BARC is by plasma etching. Plasma etching often causes thinning of the photoresist layer. Therefore, the pattern on the photoresist layer may be destroyed or become untransferred to the substrate layer. Plasma etching can also cause damage to the substrate and 144126.doc 201027261 thus 'v sounds the performance of the final device. In addition, the extra surpassing step for removing material adds cost and difficulties in processing lithography practices. One way to solve this problem is to use a wet-developable BARC. After exposure of the photoresist layer by the patterned mask, the exposed areas become wet developable, and then removed with an aqueous developer to reveal the desired trenches and/or Hole pattern. The underlying wet _ developable BARC coating is removed at the same time during this development step, thereby eliminating the need for an additional plasma surname step. The organic wet-developable ARC material has been made up of polyamic acid to form polyamine to form the desired solubility properties of this type of BARC with a fairly limited temperature window. It is also difficult to effectively control other organic BARCs comprising at least one unit having an acid labile group, a lactone or a maleimide. However, none of these wet-developable organic BARC materials have the required dry-anti-scratch for BARC for subsequent pattern transfer. Φ This invention relates to a wet etchable anti-reflective coating for lithography made from a carboxyl functional sesquiterpene oxide resin. The carboxyl functional sesquiterpene oxide resin forms an excellent spin-on film and is resistant to organic solvents such as PGMEA and 2-hePtonene, but is wet when cured at 25 (rc or below -250 C) The invention can be etched. Further, the ARC manufactured from the carboxyl functional sesquioxane resin exhibits excellent dry etching resistance. [Invention] The present invention relates to a wet type which can be manufactured from a sesquioxane resin. Etching 144126.doc 201027261 Antireflective coating 'The sesquiterpene oxide resin is composed of the following units. (Ph(CH2)rSiO(3.X)/2(〇R,)x)m (HSiO(3.x )/2(〇R,)x)„ (MeSiO(3-x)/2(〇R,)x)〇(RSiO(3-x)/2(〇R')x)p

(RSiCV^ORW where Ph is a phenyl group, Me is a methyl group; R is a hydrogen atom or a hydrocarbon group containing fluorene to 4 carbon atoms; and R is selected from a carboxylic acid group or a carboxylic acid forming group, which is defined by A sufficient amount of carboxylic acid groups are present after curing to render the resin wet etchable, and R is selected from substituted phenyl, ester, polyether groups; mercapto groups, sulfur-containing organic functional groups, hydroxyl-forming groups, Aryl sulfonate group' and reaction

Or curable organic functional group; and have a value of 〇, i, 2, 3 or 4; X has a value of 〇, 1 or 2; wherein the resin has a value of 〇95 to ;95; n has 0.05 to The value of 0.95; the value has a value from 〇 to 〇 95; ρ has a value of 〇〇5 to 〇5, q has a value of 〇 to 0.95; and the claw is cut + the mouth is called ^^. When the resins are used in an antireflective coating, they can be cured in any minute without any additives and at a temperature of 250 C or less. The cured films exhibit excellent solvent resistance (i.e., pGMEA). The cured films are wet etchable and can be easily removed with an alkaline developer such as TMAH and/or a stripper such as a fluoride based stripping solution (e.g., ne_89 and CCT_1). [Embodiment] A sesquiterpene oxide resin which can be used to form an antireflection coating layer is composed of the following units: 144126.doc 201027261 (Ph(CH2)rSiO(3-x)/2(OR 丨)x)m (HSiO (3.X)/2(〇R')x)„(MeSiO(3-x)/2(OR 丨)x)0 (RSiO(3.x)/2(OR,)x)p (RlSiOi3. x)/2(OR')x)q where Ph is a phenyl 'Me methyl group; R' is a hydrogen atom or a hydrocarbon group having from 1 to 4 carbon atoms; and R is selected from a carboxylic acid group or a carboxylic acid. a group having a condition of 0 having a sufficient amount of carboxylic acid groups after curing to render the resin wet etchable; and R1 being selected from substituted phenyl, ester, polyether groups; sulfhydryl, sulfur-containing organic a functional group, a hydroxyl group, an aryl sulfonate group, and a reactive or curable organofunctional group; and r has a value of 〇, 1, 2, 3 or 4; X has a value of 0, 1 or 2; Wherein 'm has a value of 〇 to 〇; η has a value of 〇·〇5 to 0·99; 〇 has a value of 〇 to 0.95; p has a value of 〇.〇1 to 0.5, q has 〇 to 〇.5 value, and m+n+o+p+q«l. Generally, 'm has a value of 0.05 to 0.25, or 〇.〇5 to 〇·ΐ5. 'n has a value of 0.15 to 0.80, or a value of 0.2 to 0.75. In general, '〇 has a value of 0.25 to 0.80, or a value of 0.4 to 0.75. Generally, 'Ρ has a value of 0.015 to 0.35, or 0.025 to a value of 0.25. In general, q has a value of 0 to 0.15, or a value of 0 to 0.1. R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R, for example, anthracene, methyl group, Ethyl, propyl, isopropyl and butyl. In the resin, the 'R-carboxylic acid group or the carboxylic acid forming group is defined in the absence of a thermal acid generator and/or a photoacid generator. Next, a sufficient amount of carboxylic acid groups are present after curing to render the resin wet etchable. Wet 144126.doc 201027261 etchable means removing the cured coating with an experimental developer and/or etching solution. Examples of acid groups are those having the formula _r2c(0)oh, wherein R2 is selected from alkylene groups having 1 to 1 carbon atoms. Examples of carboxylic acid forming groups are those having the formula _R2c(〇)OR3, wherein R2 is selected from the group consisting of an alkylene group having 1 to 10 carbon atoms and a protecting group for R3. The protecting group is an organic or a decyl group. The group 'clears under acidic conditions to form the corresponding carboxylic acid group. The protecting group can be exemplified by, but not limited to, a tert-butyl group, a tridecyl decyl group, an acid anhydride group, a sulfonyl thioacetate, a benzoquinone oxygen. Baseline esters, diphenyl decyl esters, p-methoxy phenoxy acetoacetate, and others. Many protecting groups are described in Greene and Wuts, "pr〇tective groUpS in 〇rganic Synthesis" Third edition, pages 369 to 453. R1 is selected from substituted strepyl, ester, polyether, mercapto, sulfur-containing organic functional groups, hydroxyl generating groups, arylsulfonate groups, and reactive or curable organic functional groups. The substituted phenyl group contains at least one of 11 〇-,]^^0-, Me-, Et-, C1- and/or other substituents. The ester group can be any organic substituent containing at least one ester functional group. Examples of useful ester groups herein are -(CH2)2-0-C(0)Me and -(CH2)2-C(0)-0Me. A polyether group is an organic substituent having a hydrocarbon unit bonded by an oxygen atom, which is represented by, but not limited to, the following structure: -(CH2)a[0(CH2)b]c〇R4, wherein a = 2 to 12, · b = 2 to 6; c = 2 to 200; R4 = H, alkyl, or other organic group. Examples of useful polyether groups are -(CH2)3-(OCH2CH2)c-OMe '-(CH2)3-(OCH2CH2)c-OH and -(CH2)3-(OCH2CH2)7-OAc and -(( CH2)3-(OCH2CH2)c-OC(0)Me. The fluorenyl group has the formula HS(CH2)d-, where d has a value from 1 to 18, such as 巯 144126.doc 201027261 propyl, decylethyl and fluorenylmethyl. The aryl sulfonate group has the formula R5o-so2-Ph-(CH2)r-, where R5 is an argon atom, an aliphatic group or an aromatic group and r has a value of ruthenium, 1, 2 or 4 or 4. The aryl sulfonate group can be exemplified by, but not limited to, h〇_s〇2_

Ph-(CH2)r- or (CH3)2CH0-S02-Ph-(CH2)r-. Reactive or curable organic functional groups can be exemplified by, but not limited to, alkenyl groups (such as vinyl and allyl groups), epoxy groups (such as glyceroloxypropyl and epoxycyclohexane groups), and acrylate groups ( Typical processes such as methacryloxypropyl, acryloxypropyl and other hydrazines for the production of carboxyl functional sesquiterpene resins involve the hydrolysis and condensation of suitable halo or alkoxysilanes. Hydrolysis and condensation of a mixture of phenyltrichloromethane, dioxane, a carboxylic acid group and/or a carboxylic acid forming group, a decane, methyltrichlorodecane, and optionally other organofunctional trichloromethane. This method may cause residual _OH and/or _〇R due to incomplete hydrolysis or condensation, and is retained in the sesquioxane resin. If sesquiterpene oxide resin contains _〇R, the unit of the group If the total amount exceeds the centromere, the resin may be gelatinized and unstable. Generally, the φ a 'sesquioxane resin contains 6 to 38 mol% of the unit containing _〇r' groups, or Less than 5 mol%' or less than 1 mol%. The sesquiterpene oxide The resin has a weight average molecular weight in the range of 5 〇〇 to 200,000, or in the range of 5 〇〇 to 1 〇〇, 〇〇〇 or in the range of 700 to 30,000, by gel permeation chromatography Method, using RI detection and polystyrene standard determination. A method for preparing a decane resin comprises reacting water, HSiX3, RSiX3, and optionally MeSiX3, phSiX3, or RlsiX3 in an organic solvent. Hydrolyzable groups or other hydrolyzable groups independently selected from α, Br, Ch3C〇2_, alkoxy_〇 &, 144126.doc 201027261. The decane useful herein may be exemplified by, but not limited to, HSi (OEt) 3) HSiCl3, PhCH2CH2SiCl3, and

PhSiCl3, MeSi(OMe)3, MeSiCl3, WSiCb and WsKOMeA, wherein R is as defined above, Me represents a methyl group, Et represents an ethyl group and ph represents a stupid group. A scouring furnace having a carboxylic acid group and/or a carboxylic acid forming group and which can be used for preparing a sesquiterpene oxide resin can be exemplified by (but not limited to): (ΜεΟ) 33ί-((:Η2)2-(: ΟΟιΒιι (MeO)3Si-(CH2)d-(OCH2CH2)e-COOtBu(MeO)3Si-(CH2)2-COO-SiMe3(MeO)3Si-(CH2)d-(OCH2CH2)e-COO-SiMe3

And

Wherein Me is a methyl group, and the lBu-based tertiary butyl group g has a value of 2 or 3 and h has a value of from 1 to 10. The water content of the reaction is usually 0.5 144 126.doc 201027261 to 2 moles of water per mole of molybdenum reactant, or χ.5 to 丨5 moles of water per mole of mordenane reactant. Within the scope. The time to form the sesquioxanese resin depends on a number of factors such as temperature, the type and amount of decane reactant, and the amount of catalyst, if any. Preferably, the reaction is carried out for a sufficient period of time such that substantially all of the groups undergo a hydrolysis reaction. In general, the reaction time is from a few minutes to a few hours, or 1 knives to 1 hour. The reaction for producing the sesquioxanese resin can be carried out at any degree / m degree as long as it does not cause significant gelation or solidification of the sesquioxane resin. The reaction temperature is generally at 25. . To the range H of the reflux temperature of the reaction mixture, the reaction is carried out by heating under reflux for 10 minutes to 1 hour. 6 The reaction step comprises hydrolyzing and condensing the money component for two hours to facilitate the reaction of the π into a catalyst. The catalyst can be a base or an acid such as a mineral acid. Useful mineral acids include, but are not limited to, HCl, HF, Chat 3, and H2S 〇 4', of which _ is yang. Or the benefits of other volatile acids

The volatile acid can be easily removed from the composition by stripping after the reaction is carried out + A B . The amount of catalyst depends on the bridge, /, and the biomass. The amount of the catalyst is based on the total weight of the reaction mixture, generally 0. 〇 5 wt% to 1 wt%. The Λ/丨烧 reactant is insoluble in water or slightly soluble in water. In this connection, the reaction is carried out in an organic solvent. The organic solution is stored in any amount sufficient to dissolve the decane reactant. In general, the organic solvent is present in an amount of from 1 to 99 based on the total amount of the reaction. / ... . , or 70 to 90% by weight. The organic solvent that can be used can be exemplified by (not limited to) a saturated aliphatic compound (such as n-decane, hexane, n-heptane, /, octane), a % aliphatic compound (such as ring 144126.doc 201027261 pentane and ring) Affiliation), aromatics (such as benzene, toluene, diphenylbenzene, mesitylene); ethers (such as tetrahydrofuran, dioxane, ethylene glycol diethyl ether, ethylene glycol dimethyl ether); Such as mercaptoisobutyl ketone (oxime) and cyclohexanone); halogen-substituted alkanes (such as tri-ethane); halogenated aromatics (such as bromobenzene and gas benzene); esters (such as propylene glycol monomethyl) Ethyl ether acetate (PGMEA), isobutyl isobutyrate and propyl propionate). Useful polyoxyl solvents can be exemplified by, but not limited to, cyclodecane oxides such as octylcyclotetraoxane and decylcyclopentaoxane. A single solvent or a mixture of solvents can be used. In the method for producing a sesquioxane resin, after the reaction is completed, the volatile matter can be removed from the sesquioxane resin solution under reduced pressure. Such volatile materials include by-product fermentation, excess water, catalyst hydrochloric acid (chloro decane path), and solvents. Methods for removing volatile materials are well known in the art and include, for example, distillation or stripping under reduced pressure. After the reaction is completed, the catalyst can be removed as needed. Methods for removing catalysts are well known in the art and include neutralization, stripping or water washing or combinations thereof. The catalyst can negatively affect the life of the sesquioxane resin (especially when in solution), so it is recommended to remove it. In order to increase the molecular weight of the sesquioxane resin and/or improve the storage stability of the sesquioxane resin, an extended time reaction should be carried out from 4 (TC heating to the reflux temperature of the solvent). a thickening step"). The thickening step can be carried out after the reaction step or as part of the reaction step. Typically, the 5' step is carried out in the range of 10 minutes to 6 hours in the range of 144126.doc 201027261, or In the range of 20 minutes to 3 hours. After the reaction for producing the sesquiterpene oxide resin, a large number of optional steps can be carried out to obtain a semi-stone oxide resin in a desired form. For example, _ §, The solid form of sesquiterpene oxide can be recovered by removing the solvent. The method of removing the solvent by shawl is not a critical step and many methods are known in the second (for example, distillation under heating and/or vacuum). If the sesquiterpene oxide resin is recovered as a solid, the resin may be redissolved in the same or other solvent as needed to prepare special money. Or, for example, if a different solvent, in addition to the reaction In addition to the solvent used, the solvent exchange required for the final product can be accomplished by adding a second solvent and removing the first solvent through the vaporizer. In addition, the concentration of the resin in the solvent can be removed by removing some solvent or Adjusted by adding another amount of solvent. Another method for producing a sesquiterpene oxide resin comprises: grafting a corresponding monomer comprising a carboxylic acid and/or a carboxylic acid forming group to the starting sesquiterpene Above the oxyalkylene resin. A typical method for grafting the corresponding monomer onto the starting sesquiterpene oxide resin is by subjecting the carboxyl group-containing olefin to Si-H in the presence of a transition metal catalyst. Hydrogenation of the sesquioxane resin. The carboxy-containing olefins useful herein include organic molecules containing a double bond and a carboxy group *_C〇〇R3, wherein R3 is as described above. The group containing the county can be exemplified. Is a carboxylic acid (R3=H), a carboxylic acid anhydride or a carboxylic acid ester. When the carboxyl group-containing group is a carboxylic acid vine group, it has a protected organic group which may be cleaved under the reaction conditions. To obtain the corresponding carboxylic acid. The carboxy-containing olefins useful herein include (but are not limited to ): CH2=CH-(CH2)g-COOR3 144126.doc •13· 201027261 where R3 can be lBu, SiMe3, SpBuMez, or CPh3; and g=0 to 8; CH2=CH-(CH2)g-COO -CH2-OMe where m = 0 to 8; CH2=CH-(CH2)g-(OCH2CH2)h-COOR3 where R can be Au, SiMe3, SfBuMe, or CPh3; g = 〇 to 8 and h has a value between 1 and 10; or

The SiH-containing sesquiterpene oxide resin useful in the manufacture of sesquioxane resin is composed of the following units: (Ph(CH2)rSiO(3-X)/2(〇R,)x)m ( HSiO(3-x)/2(〇R')x)n" (MeSiO(3-x)/2(〇R,)x)0 (R SiO(3_x)/2(〇R')x)q Wherein Ph is a phenyl group, a Me-based fluorenyl group; R' is a hydrogen atom or a hydrocarbon group of 1 to 4 carbon atoms; and R1 is selected from a substituted phenyl group, an ester group, a polyether group; An organofunctional group of a sulfur, a hydroxyl group, an arylsulfonate group, and a reactive or curable organofunctional group; and r has a value of 〇, i, 2, 3 or 4, and X has 0, 1 or 2 a value; wherein m has a value of 〇 to 〇.9〇 in the resin; η" has a value of 〇.1〇 to 1; 〇 has a value of 〇 to 〇95; q has a value of 〇 to 0.5; and m +n&quot; + 0 + qf«i. 144126.doc -14- 201027261 In general, m has a value of 0.05 to 0.25, or a value of 0.05 to 0.15. In general, η&quot; has a value from 0.165 to 0.95, or a value from 0.225 to 0.95. In general, 〇 has a value of 0.25 to 〇.8〇, or a value of 0.25 to 0.75. In general, 'q has a value from 〇 to 〇 15, or a value from 〇 to 〇丨. The drum-containing olefin and the Si-H-containing sesquiterpene oxide resin are reacted in the presence of a transition metal catalyst. Useful transition metal catalysts can be selected from the various φ hydride calcining catalysts known to promote the reaction of ethylene functional groups with hydrazine-bonded hydrogen atoms. Suitable transition metal catalysts can include compounds and complexes containing platinum and rhodium. Platinum catalysts such as acetonitrile pyroplatin or gas platinum acid are representative of such compounds and are suitable for use. A typical transition metal catalyst is a divinyltetramethyl-alkali-oxygenated gas-acid complex, which is terminated with a dimethylvinyl methoxy group. The polydimethyloxane was diluted ten times. The amount of the carboxyl group-containing olefin relative to the Si-H-containing sesquioxane resin is generally such that the final resin contains 5 to 99 mol% (Hsi〇(3 x)/2(〇R,)x) and ι ❿ to 50% by mole (RSi〇(3.x)/2(0R,)x), or 15 to 8〇% by mole (HSl〇(3-x)/2(OR,)x)&amp; L5 Up to 35 mol% (RSi〇(3 y, 2 (〇R, D, or 20 to 75 mol. / (4) "(10)^ and even "Mole%" (RSi〇(3-xV2(OR ')x). The amount of transition metal catalyst used is generally present in a quantity based on one of the total weight of the sulfhydryl-containing dilute hydrocarbon and the Si_H-containing sesquiterpene to provide 2 ppm, or 5 to 2 ppm. Transition metal (ie R). The sesquioxane resin is generally applied from a solvent. Solvents which may be used include, but are not limited to, especially methoxy-2-propanol, propylene glycol monomethyl acetate, Γ_丁内_, and Ring (10). The ARC composition generally comprises a base 144126.doc -15- 201027261 from 1% by weight to 99.9% by weight, or from 8〇 to 95% by weight, based on the total weight of the ARC composition. The anti-reflective coating is obtained by doubling the resin, solvent and, if necessary, The additive is formed by mixing together. The anti-reflective coating is formed on an electronic device by a method comprising: (A) applying an ARC composition to an electronic device, the arC composition comprising: (i) half Shixi Oxygen Burning Resin consisting of the following units: (Ph(CH2)rSiO(3.x)/2(〇RI)x)m (HSiO(3-x)/2(OR,)x)n (MeSiO (3-x&quot;2(〇R')x)0 (RSiO(3-x)/2(〇R')x)p (R1SiO(3-x)/2(ORi)x)q in this Ph system Phenyl, Me is a methyl group; R is a hydrogen atom or a hydrocarbyl group of fluorene to 4 carbon atoms, and R is selected from a carboxylic acid group or a carboxylic acid forming group, which is defined by the presence of a sufficient amount of carboxylic acid after curing. The base is such that the resin is wet etchable; and R1 is selected from the group consisting of substituted phenyl, ester, and (iv) groups; weigen, oxime-containing organic functional groups, hydroxyl-forming groups, aryl sulfonic acids, or curable organic functional groups. Base: and (4) The value of ^ should be 0, 1 or 2; where m has a value of 〇 to 〇9〇 in the resin. n has a value of 〇.〇5 to 〇.99; ❹95 value; ρ has a value from 〇 to 〇$; q has a value from 0 to 0.5; and m+n+〇+p+qa;1; and (ii) dissolve And 144126.doc 201027261 (B) removing the solvent and curing the sesquioxanated resin to form an anti-reverse coating on the organic device. The anti-reflective coating composition is applied to an electronic device for manufacturing Coated substrate. The solvent is removed and the sesquioxane resin is cured to produce an anti-reflective coating on the electro-device. In general, the electronic device is a semiconductor device intended for use in a semiconductor device, such as a germanium-based device and a gallium arsenide-based device. Generally, the device includes at least one semiconductor layer and a plurality of other layers including different conductive, semi-conductive, or insulating materials. Specific methods of applying the ARC composition to an electronic device include, but are not limited to, spin coating, dip coating, spray coating, flow coating, screen printing, and other methods. The preferred method of application is spin coating. In general, coating involves rotating the electronic device at a speed of 1 Torr to 2 Torr (111) and applying an ARC composition to the surface of the rotating electronic device. The solvent is removed and the sesquioxane resin is cured to form an anti-reflective coating on the electronic device. Curing generally involves heating the coating to a temperature high enough for sufficient duration to cause curing. Curing occurs when sufficient cross-linking occurs such that the sesquiterpene oxide resin is substantially insoluble in its solvent at the time of application. "Curing can occur, for example, by coating the electronic device at 80 C to 450 ° C. Heat for 0.1 to 60 minutes, or heat the coated electronics for 0.5 to 5 minutes, or at 20 Torr. (: to 25 〇. (: The coated electronic device is heated for 0.5 to 2 minutes. Any heating method can be used in the curing step. For example, the coated electronic device can be placed in a quartz tube furnace, convection oven Or statically placed on a hot plate. 144126.doc 201027261 To protect the coated composition of the sesquiterpene oxide resin from reacting with oxygen or carbon during curing, the curing step can be carried out in an inert atmosphere. This includes, but is not limited to, nitrogen and argon. “Inert” means that the environment contains less than 50 ppm and or less than 1 ppm of oxygen. The pressure at which the curing and removal steps are carried out is not a critical factor. Pressure or superatmospheric pressure can also be carried out, but the curing step is generally carried out under atmospheric pressure. Generally speaking, the antireflective coating is insoluble in the photoresist casting solvent after curing. These solvents include, but are not limited to, esters. And ethers such as propylene glycol monomethyl ether acetate (PGMEA) and ethyl ethoxy propionate (EPpp insoluble means that when the anti-reflective coating is exposed to a solvent, the thickness of the coating is almost or after 1 minute of exposure. There is no loss at all. In general, the coating thickness loss is less than 10% of the coating thickness, or less than 7.5% of the coating thickness. The invention also relates to a method comprising: (a) on a substrate Forming an anti-reflective coating; (b) forming an anti-surname coating on the anti-reflective coating; (0 causing the resist to receive radiation; (d) developing the resist and the anti-reflective coating; wherein the anti-reflection The coating is made from a sesquioxane resin consisting of the following units: (Ph(CH2)rSiO(3-x)/2(〇R')x)m (HSiO(3) .x)/2(OR')x)n (MeSiO(3-x)/2(OR,)x)0 (RSiO(3-X)/2(〇R')x)p (R, SiO( 3.x)/2(〇R,)x)q 144126.doc •18· 201027261 Here Ph is a phenyl group, Me is a f group; R is a hydrogen atom or a hydrocarbon group of 丨 to 4 carbon atoms'·R Is selected from a carboxylic acid group or a carboxylic acid forming group, which is defined by the presence of a sufficient amount of carboxylic acid groups after curing to render the resin wet etchable, and - and R1 is selected from substituted phenyl, vinegar Base, poly-based; sulfhydryl, sulfur-containing. Organic functional group, thiol-forming group, thiol-based vinegar group, and reactive or curable organic functional group Having a value of 〇, 1, 2, 3 or 4; χ having a value of 0, 1, or 2; wherein the guacamper has a value of 〇 to 〇9〇 in the resin; η has a value of _ 0.05 to 0.99, · 〇 Having a value from 〇 to 95; ρ has a value of 〇〇1 to (^; q has a value of 0 to 0.5; and m+n+〇+p+qwl. The antireflection coating is shaped as described above. An anti-smudge coating is formed on the anti-reflective coating. The anti-surname coating can be formed using any known anti-surname material and methods for forming. In general, the anti-syndication (4) is applied from a solvent solution in a similar manner to the method of making an anti-reflective coating herein. The anti-(iv)i coating can be bake to remove any solvent. Depending on the baking source used, the total baking is generally carried out by heating the coating from 9 (rc to 13 〇t for several minutes to one hour or longer). After the resist layer is formed, it is exposed to Radiation, ie υν, χ_ ray, electron beam 'EUV, etc. Generally, use ultraviolet radiation with a wavelength of (5) nm to 365 nm or use ultraviolet radiation with a wavelength of 157 ^(7) or 打^. These include mercury, mercury/gas, and gas lamps. The preferred source is KrF excimer laser (248 nm) or ArF excimer laser 093 nm). If longer wavelength radiation (eg 365 nm) is used, it is recommended to add a sensitizer to the photoresist composition to enhance the absorption of radiation. The complete exposure of the photoresist composition can generally be achieved with a light shot of less than 1 〇〇 mJ/cm2, or 144126.doc.] 9· 201027261 is achieved with a shot of less than 50 mJ/cm. In general, the resist layer is exposed through the mask to form a pattern on the coating. When exposed to radiation, the radiation is absorbed by the acid generator in the resist composition to form a free acid. When the resist composition is a positive anti-surname agent, the free acid can cause separation of the acid-separable groups of the anti-surname agent if heated. When the field resist is a negative resist, the free acid can cause the crosslinking agent to react with the resist and thereby form an insoluble region of the exposed anti-touching agent. After the anti-surname layer is exposed to radiation, the resist composition typically undergoes post-exposure baking, which is heated to 30 ° C to 200. (: within the temperature range, or 75C to 150C - short period of time, usually 3 sec to 5 minutes, or 6 〇 to 90 sec. Use exposed anti-reagent and anti-reflective coating with appropriate developer or The stripping solution is removed to create an image. Since the anti-reflective coating is wet etchable, it can be removed while the exposed resist is removed, and thereby removing the separate etching steps to remove In addition to the need for an anti-reflective coating, suitable developer solutions typically comprise an aqueous base solution, preferably an aqueous solution containing no metal ions, and optionally an organic solvent. Those skilled in the art will be able to select a suitable developer solution. Standard industry developer solutions can be exemplified by, but not limited to, organic metals such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium sulphate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine. N-propylamine), secondary amines (such as diethylamine, and di-n-butylamine), tertiary amines (such as triethylamine and methyldiethylamine), and amines (such as dimethylethanolamine and triethanolamine) a quaternary ammonium salt (such as tetramethyl hydrogen) Ammonium oxide, tetraethylammonium hydroxide and choline), and cyclic amines (such as pyrrole and piperidine). In general, the use of quaternary ammonium salt 144126.doc -20- 201027261 'liquid" such as four 曱Suitable ammonium hydroxide (TMAH) or choline. Suitable vapor-based stripping solutions include, but are not limited to, NE_89 &amp; cCT_i. After the exposed film has been developed, the residual resist is typically washed with water ("Pattern J To remove any residual developer solution. The pattern produced in the resist and anti-reflective coating can then be transferred to the material of the underlying substrate. In coated or double-layered photoresist, this will involve To transfer the pattern through the coating that may be present and through the underlying layer to the substrate. _ Direct transfer to the substrate in a single layer of photoresist. In general, the pattern is by using reactive ions such as oxygen, plasma And/or oxygen/sulfur dioxide plasma etching for transfer. Suitable plasma appliances include, but are not limited to, electron cyclotron resonance (ECR), spiral wave, inductively coupled plasma (ICp), and transmission coupled electrical Slurry (TCP) system. Etching technology Those skilled in the art and familiar with the art are familiar with different commercially available equipment. Additional steps or removal of the resist film and residual anti-reflective coating can be used to make a device having the desired architecture. The antireflective coating composition of the present invention can be used to fabricate patterned material layer structures, such as metal lines, holes or vias for contact, insulating portions (such as damascene trenches or shallow trench isolation), for capacitor structures. Grooves, etc., etc., can be used to design integrated circuit devices. These methods for fabricating such features are well known in the art. Solid-state displays include anti-reflection... 1 is shown in this method. An anti-reflective coating is formed on the anti-reflective coating. The resist is applied by exposure using an exposure device and a mask, followed by exposure (PEB). The anti-reagent layer is then exposed using a metal-detecting solution. More (,, Luo I44l26.doc 201027261 development). The antireflective coating is then removed by a typical method such as RI (money engraving) to expose the substrate. The substrate is then subjected to a general process, such as substrate etching and/or ion implantation. Figure 2 shows a wet patterning process using an anti-reflective coating as described herein. The method includes forming a resist coating on the anti-reflective coating. The anti-drug coating is exposed using an exposure apparatus, followed by exposure to post-bake (PEB). The resist coating and the anti-reflective coating are then simultaneously wet developed using an inert solution. The substrate is then subjected to a general process such as substrate etching and/or ion implantation. EXAMPLES The following examples are included to illustrate embodiments of the invention. Those skilled in the art will appreciate that the techniques disclosed in the examples below represent techniques discovered by the inventors to function well in the practice of the present invention. However, it will be apparent to those skilled in the art that <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; All percentages are by weight. /. The form. The structures given in Examples 1 to 6 are based on the theoretical structure of the reactants. Example 1 T (PhViQT('.2〇T,). 625 T (PS'〇75 Take 445.1 g of propylene glycol thioglycolate, 3〇89^ of 3_(ethoxylated) Peric acid anhydride (〇1〇1 mol), 2862 g of phenyl trioxane (〇135 mol), 126 4 g of decyl trioxane (〇·846 mol), and 36·65 g of trichloromethane (0.271 mol) was charged into the reactor to set the jacket temperature to 25. (:. Stir the solution vigorously. Place 1448〇g of 144126.doc 201027261 PGMEA and 54.1 g of deionized water. In the flask, the mixture of PGMEA and water was vigorously stirred until all the water was dissolved in PGMEA. Next, PGMEA/water solution was added to the reactor under nitrogen for 1 hour under vigorous stirring of the reactants. The mixture in the reactor was washed three times with DI water (2 x 571 g). The solution was then stripped after addition of 120 g of ethyl acetate (EtOH) to give a clear PGMEA solution. The solution was diluted to 10 weights by adding more PGMEA. % and subsequently filtered through a 0.2 mm Teflon filter. GPC (for polystyrene): Mw = l 1300, Mw / Mn = 2.70. Example 2 rp(Ph) - γ(Η) rp(Me) T(PSA) 丄0.05 1 0.50 丄0.425 丄0.075 Take 672.5 g of propylene glycol methyl acetate (PGMEA), 11.42 g of 3-(triethoxy) Alkyl propyl succinic anhydride (0.038 mol), 15.78 g of phenyl trioxane (0.075 mol), 95.29 g of decyl trichlorodecane (0.638 mol), and 101.59 g of trichloro Put decane (0.750 mol) into the reactor. Set the jacket temperature to 25 ° C. Stir the solution vigorously. Place 1080 g of PGMEA and 59.4 g of deionized water in the flask. Stir the mixture of PGMEA and water vigorously. Until all the water is dissolved in PGMEA. Next, PGMEA/water solution is added to the reactor under nitrogen for 1 hour under vigorous stirring of the reactants. After the addition is completed, the mixture in the reactor is treated with DI water (2x500). g) Wash three times. Then strip the solution after adding EtOH (120 g) to obtain a clear PGMEA solution. Dilute the solution to 10 wt. 0/〇 by adding more PGMEA and then via 0.2 mm Teflon. Filter filtration. GPC (for polystyrene): Mw=44300, 144126.doc -23- 201027261

Mw/Mn=5.99 〇 Example 3 D (PhEt)

Styrene (7.29 g, 0.07 mol) and butyl methacrylate (32.71 g '0.23 mol) were added to 200 mL of toluene containing sesquiterpene oxide resin (Mn = 2200, 37.10 g, 0.7 In a flask of Mohr, a platinum catalyst was added thereto. The mixture was stirred and irradiated with a uv lamp at room temperature. After 18 hours, the volatiles were removed at 40 ° C to give the title resin as a viscous oil. The resin was dissolved in PGMEA to give a 1% by weight solution and the solution was filtered through a 0.2 mm Teflon filter. GPC (relative to polystyrene): Mw = 4890, Mw / Mn = 2.44; Example 4 T (PhEt) 〇〇 7 ΐΓ (Η) 〇 Tf (CH2) 3COOtBu)] 〇i9 will be styrene (3.65 g, 0.035 Mo Ears and tert-butyl crotonate (1 7 〇g, 0.115 mol) were added to a flask containing sesquiterpene oxide resin (Mn = 2200, 26.5 g, 0.5 mol) in 2 Torr toluene. The platinum catalyst is then added to it. The mixture was stirred and refluxed overnight. The volatile hydrazine was removed at 40 ° C to obtain a viscous oil. The resin was dissolved in PGME A to give a 1% by weight solution and the solution was filtered through a 2.2 mm Teflon filter. GPC (for polystyrene): mw=5 73 0, Mw/Mn=2.21; Example 5 T(PhEt)〇.〇7T(H)〇.7〇T[(CH2)3COOtBu]〇23 styrene ( 3.65 g '0.035 mol) and tert-butyl crotonate (14·22 g '0·095 mol) added to 1 〇〇mL toluene containing sesquiterpene oxide resin M4126.doc -24- 201027261 ( In a flask of ^11=11,800,20 §, 0.38 mol), a platinum catalyst was added thereto. The mixture was stirred and refluxed overnight. Rotary evaporation at 40 ° C to obtain a viscous oil. The resin was dissolved in PGMEA to give a 10% by weight solution and the solution was filtered through a 0.2 mm Teflon filter. GPC (polystyrene): Mw = 15,300, Mw / Mn = 2.78; Example 6

T(Ph)〇1 T(H)〇2 T(Me)〇6 j((CH2)3COOtBu)〇J Adding butyl butenoate (3.26 g, 0.022 mol) to 100 mL of toluene TXPhViTCHVJCMe). In a resin (20 g, 0.38 mol) flask, a platinum catalyst was added thereto. The mixture was stirred and refluxed overnight. The volatile matter was removed by rotary evaporation at 40 ° C to give a white solid. The resin was dissolved in PGMEA to give a 10% by weight solution and the solution was filtered through a 0.2 mm Teflon filter. GPC (p-phenylene): Mw = 12,450, Mw / Mn = 2.95 实例 Example 7 The film coating on the wafer was treated with a Karl Suss CT62 spin coater. The resin PGMEA solution was first filtered with a 0.2 micron Teflon filter and then spin coated onto a standard single-sided four inch polished low resistance wafer or double side polished FTIR wafer (rotation speed = 2000 rpm; acceleration = 5 000 ; time = 20 seconds unless otherwise indicated. The film was cured on a hot plate at a temperature of 25 °C. The PGMEA and TMAH losses after curing were determined by film thickness changes before and after PGMEA or TMAH impregnation. The results are shown in Table 1. I44126.doc •25- 201027261

SZ&lt;N 〇〇0!&gt;· oos inch i Γη9 inch ι ε£

8 卜 9CN Μ«ΦΙ(Υ) stupid vlod ι τ 16 τ inch oi

II ε inch.6 669CN 93⁄400§ SI 06 卜 I S06 Bu B 00,6 I ΓΙΐ Z Bu inch I 6_ inch I—ιI 5 AS inch I rlnoos&lt;N Γ900_ 0.9 inch δ ais 0 03⁄4 γ γ 卜 卜 0. 0 τ s Ό Ό To-o Js.oj (vsd)h(3Eh(H)Bu(Md)Bu-0·0 Two so T 0-°:T-°'- (vsd)h(9sh(H) l· s (nsoo°0SHu

:τ°·0 τε·'°- sp {HT (S£T 2.0:Mnfl—

[(nsoou( H3)T(n) 卜(sMd)L s ez-oo,--,- =8003( H3)l 卜(H)h 03£ΐ τ 寸 5(li5tsgl-.€ 9 144126.doc 26- 201027261 [Simplified Schematic] FIG. 1 shows a conventional dry patterning process using a resist layer and an anti-reflective coating; and - FIG. 2 shows a resist layer and an anti-reflective coating as described herein. Wet patterning process.

144126.doc -27-

Claims (1)

201027261 VII. Patent Application Range: 1. A method of forming an anti-reflective coating on an electronic device, comprising: (A) applying an anti-reflective coating composition to an electronic device, the anti-reflective coating composition Including: (i) sesquiterpene oxide resin consisting of the following units: (Ph(CH2)rSiO(3-x)/2(OR')x)m (HSiO(3.x)/2(〇 R')x)n ©(MeSiO(3.x)/2(〇R,)x)〇(RSiO(3_x)/2(OR')x)p (R)SiO(3.x)/2( OR|)x)q wherein Ph is a phenyl group, Me is a fluorenyl group; R is a hydrogen atom or a hydrocarbon group having from 1 to 4 carbon atoms; and R is selected from a carboxylic acid group or a carboxylic acid forming group, and the restrictions thereof In order to have a sufficient amount of a slow acid group after curing to make the resin wet developable; and R1 is selected from substituted phenyl, ester, polyether groups; mercapto group, sulfur-containing organic functional group, hydroxyl group , an aryl carboxylic acid φ group, and a reactive or curable organic functional group; and r has a value of 0, 1, 2, 3 or 4; X has a value of ruthenium, 1 or 2; wherein in the resin, m has a value of 0 to 0.90; η has a value of 〇.〇5 to 〇·99; 〇 has a value of 〇 to 0.95; Ρ has 0. a value of 01 to 0.5; q has a value of 〇 to 0.5; and m+n+〇+p+q«i; and (Π) a solvent, and (B) remove the solvent' and the sesquioxane resin Curing to form an anti-reflective coating on the electronic device. 2. A method comprising: 144126.doc 201027261 (a) forming an anti-reflective coating on a substrate; (b) forming a resist coating on the anti-reflective coating; (c) rendering the resist Exposure to radiation; (d) developing the anti-surplus agent and the anti-reflective coating; wherein the anti-reflective coating is produced from a sesquiterpene oxide resin. The sesquiterpene oxide resin is composed of the following units: Ph(CH2)rSiO(3-x)/2(OR')x)m (HSiO(3_x)/2(〇R,)x)n (MeSiO(3.x)/2(OR')x)0 φ (RSiO(3-X)/2(OR,)x)p (R1SiO(3.x)/2(OR,)x)q wherein Ph is a phenyl group, Me is a fluorenyl group; R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R is selected from a carboxylic acid group or a carboxylic acid forming group, with the proviso that a sufficient amount of a carboxylic acid group is present after curing to make the resin wet developable'· and the R1 system Selected from substituted phenyl, ester, polyether; thiol, sulfur-containing organic functional group, hydroxyl generating group, aryl sulfonate group, and reactive or curable organic functional group having 〇, 1, 2, the value of 3 ® or 4; X has a value of 〇; wherein in the resin, ^ has a value of 0 to 0.90; n has 0.05 〇 has a value of 99; 〇 has a value of 〇95; Ρ has a value of 0.01 to 0.5; q has a value of 〇 to 0.5; and m+n+o+p+q«i 〇3. The method of claim 1 or 2 wherein the antireflective coating composition is applied by spin coating. The method of claim 1 or 2, wherein the method is at 8 CTC to 450. (: heating 144126.doc 201027261 0.1 to 60 minutes to remove the solvent and curing the sesquiterpene oxide resin. 5. The method of claim 1, wherein the solvent (ii) is selected from the group consisting of 1-methoxy _2-propanol, propanol mono-mercaptoacetate, γ-butyrolactone, and cyclohexanone. The method of claim 1, wherein the solvent is based on the total anti-reflective coating composition. The method of claim 1 or 2, wherein the sesquiterpene oxide resin is derived from (PhSiO(3.x)/2(〇R')x)m , (HSiO) (3-x)/2(〇R')x)„ ' (MeSiO(3.x)/2(OR')x)0 ❹ , and (RSi〇(3_x)/2(OR,)x)p a unit composition, wherein Ph is a phenyl group, a Me-based methyl group; R1 is a hydrogen atom or a nicotinyl group having from 1 to 4 carbon atoms, and R is selected from a decanoic acid group or a slow acid forming group, and the limitation is that it is cured. A sufficient amount of carboxylic acid groups are then present to render the resin wet developable, X having a value of 〇, !, or 2; wherein in the resin, m has a value of 0.05 to 0.15; n has a value of 〇·ΐ5 to 0.80; 〇 has a value of 0.25 to 0.80; ρ has a value of 0.015 to 〇.25; and m+n+0+pfta. The method of claim 1 or 2, wherein the sesquiterpene oxide resin is composed of ruthenium (Ph(CH2)2SiO(3.x)/2(〇R')x)m, (HSiO(3.x)/2 (〇R')x)n, and (RSiO(3_x)/2(〇R')x)p unit composition, wherein Ph is a base group, R1 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; Is selected from a carboxylic acid group or a carboxylic acid forming group, with the proviso that a sufficient amount of carboxylic acid groups are present after curing to render the resin wet developable; X has a value of 0, 1, or 2; wherein in the resin , ^ has a value of 〇.〇5 to 0.15; η has a value of 0·15 to 0.80; p has a value of 0.015 to 0.25; and m+n 士ρ»1. 9. The method of claim 1 or 2, Wherein R is -r2C(〇)〇h, wherein R2 is selected from 144126.doc 201027261 from an alkyl group having from 1 to 10 carbon atoms. 10. The method of claim 1 or 2 wherein R is -R2C (0) a mixture of 0H and -R2C(0)0R, wherein R2 is selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, and a protecting group for R3. 144126.doc